Compositions for polyurethane applications

ABSTRACT

A process comprising, consisting of, or consisting essentially of: foaming a reaction mixture containing at least one polyisocyanate and an isocyanate-reactive compound comprising at least one alkoxylated triazine-arylhydroxy-aldehyde condensate composition wherein the alkoxylated triazine-arylhydroxy-aldehyde condensate composition is a reaction product of a triazine-arylhydroxy-aldehyde condensate and at least one alkylene carbonate, is disclosed.

FIELD OF THE INVENTION

This invention relates to processes for making polymers frompolyisocyanates and isocyanate reactive materials. In particular, thisinvention relates to alkoxylated triazine-arylhydroxy-aldehydecondensate compositions useful as isocyanate reactive materials.

BACKGROUND OF THE INVENTION

Aromatic polyols are used as cross-linkers for isocyanates andisocyanurates that go into polyurethane and polyisocyanurate-basedpolymers. The largest end use for aromatic polyols is in applicationswhere insulation, flammability, and structural performance are mostimportant.

There is an increasing demand for better performing rigid polyurethanefoams that have particular flammability specifications and acceptablephysical properties. It is known that when typical rigid polyurethanefoams, particularly spray foams, are formed in thicknesses of greaterthan about 2 inches, such foams are subject to internal scorching due tohigh exotherm temperatures resulting from reactions of certainisocyanates and polyols. Internal scorching not only degrades thephysical properties of the rigid polyurethane foams rendering themunsuitable for most applications but also has the potential to causeother problems related to flammability. In addition, these typical rigidpolyurethane foams are flammable and vulnerable to burning and smoking,all of which are undesirable.

To reduce scorch, decrease flammability and smoking, many rigidpolyurethane foams include high levels of halogenated flame retardants.Although halogenated flame retardants are inexpensive, they have beenlinked to environmental concerns. Accordingly, there remains anopportunity to develop rigid polyurethane foam that has a minimum amountof halogenated flame retardants or eliminate the need to have anadditional flame retardant that resists scorching, burning, and smoking,while simultaneously having acceptable physical properties.

Novolacs are known to the polyurethane industry as aromatic polyols thattypically go into rigid polyurethane and polyisocyanurate foamapplications. The novolac polyol is said to promote intumescence (i.e.,swelling) of the rigid polyurethane foam, promotes char, decreasesscorch, and decreases flammability of the foam. The novolac polyol isalso thought to react with isocyanates more quickly than the isocyanatesreact with water thereby increasing production speed, reducing cost, andallowing the rigid polyurethane foam prepared from a novolac polyol tobe used in a wide variety of applications, especially those that requirefast foaming times.

While novolacs improve the flame retardancy of the polyurethaneformulations and offer rigidity to the foam, these materials havedrawbacks. The main challenges are the processing difficulty due to highviscosity.

Once the polyol is mixed with the isocyanates, the gel time is typically10-25 seconds so the novolac has to mix into the system quickly, whichcan be a challenge due to the inherent viscosity. In addition, theurethane bond formed by the reaction of aromatic polyol and isocyanateis reversible at certain temperatures where the aliphatic polyolreplaces the aromatic polyol. These factors can lead to decreasedperformance and difficulties in processing. While aromatic polyols offerend use benefits in polyurethanes such as flame resistance and scorchresistance they are difficult to employ in existing processes due tohigh viscosity and stability of the final product.

The current polyurethane formulations for applications such as rigidfoam require multifunctional polyols as isocyanate reactive chemicals.The common ones are carbohydrate-based polyols, which are not veryeffective when it comes to flame resistance.

Thus, there is a need for aromatic polyols having decreased viscositythat will have minimal tendency to unzip in the presence of otherpolyols, that will increase cure efficiency, resulting in a foam withimproved flammability, insulation, and mechanical characteristicscompared to foams prepared with conventional polyols.

SUMMARY OF THE INVENTION

In one broad embodiment of the present invention, there is disclosed aprocess comprising, consisting of, or consisting essentially of: forminga reaction mixture containing at least one polyisocyanate and anisocyanate-reactive compound comprising at least one alkoxylatedtriazine-arylhydroxy-aldehyde condensate composition wherein thealkoxylated triazine-arylhydroxy-aldehyde condensate composition is areaction product of a triazine-arylhydroxy-aldehyde condensate and atleast one alkylene carbonate.

DETAILED DESCRIPTION OF THE INVENTION

Embodiments of the invention are directed to alkoxylatedtriazine-arylhydroxy-aldehyde condensates, methods for making thealkoxylated triazine-arylhydroxy-aldehyde condensates, and the use ofalkoxylated triazine-arylhydroxy-aldehyde condensates in the manufactureof polyurethane and polyisocyanurate resins.

An alkoxylated triazine-arylhydroxy-aldehyde condensate is formed byreacting a triazine-arylhydroxy-aldehyde condensate with an alkylenecarbonate.

Any suitable triazine-arylhydroxy-aldehyde condensate can be used in thereaction with the alkylene carbonate. In various embodiments, thetriazine-arylhydroxy-aldehyde condensate is formed from a reactionmixture of a triazine monomer, an arylhydroxy monomer, and an aldehydemonomer. In various embodiments, the triazine-arylhydroxy-aldehydecondensate is a novolac.

The triazine monomer can be a triazine compound or a triazinederivative. An example of a triazine compound is melamine and an exampleof a triazine derivative is a melamine derivative.

Suitable compounds that can be used as the triazine monomer includecompounds selected from the group of aminotriazine,4-methyl-1,3,5-triazine-2-amine, 2-amino-4,6-dimethyl-1,3,5-triazine,melamine, hexamethoxymethylmelamine, hexamethylolmelamine, guanamine,acetoguanamine, propioguanamine, butyroguanamine, benzoguanamine,vinylguanamine, 6-(hydroxyphenyl)-2,4-diamino-1,3,5-triazine, andcombinations thereof.

The arylhydroxy monomer can be any suitable aromatic monomer with one ormore hydroxyl groups per molecule, such as a monohydroxy, dihydroxy or atrihydroxy benzene. They can be mononuclear or binuclear. In variousembodiments, the arylhydroxy monomer is a phenol monomer compound.Phenol monomer compounds having at least one ortho or para positionavailable for bonding are preferred compounds. The phenol monomercompound can be an unsubstituted or substituted compound, for example,with an alkyl group, a phenyl group, a hydroxybenzene group, an alkoxygroup, and combinations and subsets thereof. The phenol monomer compoundcan also include compounds having up to about 15 carbon atoms such as upto about 8 carbon atoms. Examples of such arylhydroxy monomers include,but are not limited to phenol, cresols, xylenols, resorcinol, catechol,hydroquinone, naphthols, biphenols, bisphenols, phloroglucinol,pyrogallol or their derivatives.

The aldehyde monomer includes compounds having one or more aldehydefunctional groups (—CHO) and any compounds yielding aldehydes. Thealdehyde monomer can be represented by the formula R—CHO, and R can bean aliphatic or aromatic organic functional group. The aldehyde monomercan be a dialdehyde such as glyoxal. Suitable aldehydes include, but arenot limited to compounds selected from the group of formaldehyde,paraformaldehyde, acetaldehyde, i-butyraldehyde (isobutyraldehyde),benzaldehyde, acrolein, crotonaldehyde, salicylaldehyde,4-hydroxybenzaldehyde, furaldehyde, pyrrolaldehyde, cinnamaldehyde,trioxymethylene, paraldehyde, terephthaldialdehyde, glyoxal,glutaraldehyde and combinations thereof.

The triazine-arylhydroxy-aldehyde condensate can be comprised of avariety of triazine, arylhydroxy, and aldehyde combinations. In variousembodiments, the condensate is a melamine, phenol, and formaldehydenovolac. Further details about the triazine-arylhydroxy-aldehydecondensate and its preparation can be found in U.S. Pat. Nos. 6,239,248and 9,249,251, which are both herein incorporated by reference.

The triazine-arylhydroxy-aldehyde condensate is reacted with at leastone alkylene carbonate to form the alkoxylatedtriazine-arylhydroxy-aldehyde condensate.

The alkylene carbonate can be a variety of alkylene carbonates. Mixturesof alkylene carbonates can also be used. The general structure of analkylene carbonate is represented by Formula I, below:

In Formula I, R₁ and R₂ are each independently a hydrogen atom, an alkylgroup having 1 to 4 carbon atoms, a vinyl group, or an alkyl group with1 to 4 carbon atoms containing a hydroxyl group.

The alkylene carbonate can also be a six-membered structure, asrepresented by Formula II, below:

In Formula II, R₃, R₄, and R₅ are each independently a hydrogen atom, analkyl group having 1 to 4 carbon atoms, a vinyl group, or an alkyl groupwith 1 to 4 carbon atoms containing a hydroxyl group.

In the descriptions of the alkoxylated triazine-arylhydroxy-aldehydecondensate composition below, R₁ and R₂ in the product structuregenerally correspond to the R₁ and R₂ groups of Formula I. In variousembodiments, where a composition having the structure of Formula II isused to make the composition, R₃, R₄, and/or R₅ groups are substitutedfor the R₁ and R₂ groups. In various embodiments, the alkylene carbonatecan be selected from the group consisting of ethylene carbonate,propylene carbonate, and mixtures thereof.

The triazine-arylhydroxy-aldehyde condensate is reacted with at leastone alkylene carbonate to form an alkoxylatedtriazine-arylhydroxy-aldehyde condensate. In various embodiments,reaction conditions can include a reaction temperature in the range offrom 50° C. to 270° C. Any and all temperatures within the range of 50°C. to 270° C. are incorporated herein and disclosed herein; for example,the reaction temperature can be from 100° C. to 200° C., from 140° C. to180° C., or from 160° C. to 175° C. The reaction conditions can alsoinclude a reaction pressure in the range of from 0.01 bar to 100 bar.Any and all pressures within the range of from 0.01 bar to 100 bar areincluded herein and disclosed herein; for example, the reaction pressurecan be from 0.1 bar to 50 bar, from 0.5 bar to 20 bar, or from 1 bar to10 bar. The components can be added together in any suitable manner. Forexample, the reaction can take place in a batch system, a continuoussystem, a semi-batch system, or a semi-continuous system. In variousembodiments, the alkylene carbonate can be added slowly to moltentriazine-arylhydroxy-aldehyde condensate and then reacted until CO₂evolution has ceased.

Optionally, the reaction between the triazine-arylhydroxy-aldehydecondensate and the alkylene carbonate can take place in the presence ofa catalyst. Examples of catalysts that can be used include, but are notlimited to sodium hydroxide, potassium hydroxide, lithium hydroxide,ammonium hydroxide, magnesium hydroxide, calcium hydroxide, bariumhydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate,potassium bicarbonate, potassium phosphate, sodium phosphate, andlithium phosphate. If necessary, an organic acid such as oxalic acid,formic acid, acetic acid, trifluoroacetic acid, methane sulfonic acid,salicylic acid, or p-toluenesulfonic acid can be used to neutralize thereaction mixture.

In various embodiments, the alkoxylated triazine-arylhydroxy-aldehydecondensate compound can be represented by Formula III below.

The R₆ functional group is represented by Formula IV or Formula V. TheR₇ functional group of Formula III can be a hydrogen atom or representedby Formula IV or Formula VI.

R₈ and R₉ can each independently be a hydrogen atom, an alkyl group with1 to 10 carbon atoms, a vinyl group, a phenyl group, a hydroxyphenylgroup,  NH(Formula VI), —N(Formula VI)₂, —NH(Formula IV), —N(FormulaIV)(Formula VI), —N(Formula IV)₂, —NH(Formula V), —N(Formula V)(FormulaVI), —N(Formula V)₂, NH(Formula VII), —N(Formula VI)(Formula VII),—N(Formula VII)₂, or —NH₂.

The structures of Formulas IV, V, VI, and VII are depicted below.

In the above Formulas, R₁ and R₂ are independently a hydrogen atom, analkyl group having 1 to 4 carbon atoms, a vinyl group, or an alkyl groupwith 1 to 4 carbon atoms containing a hydroxyl group.

R₁₀ can be a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, analkyl group with 1 to 10 carbon atoms containing a hydroxyl group, aphenyl group, a vinyl group, a propenyl group, a hydroxyl-containingphenyl group, a pyrrole group, or a furanyl group.

R₁₁ and R₁₂ are each independently a hydrogen atom, an alkyl group with1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, aphenyl group, a hydoxybenzene group, or an alkyl group with 1 to 10carbon atoms with at least one carbon substituted with i) a hydroxylgroup, ii) a hydroxybenzene group or iii) a phenyl group. In variousembodiments, R₁₁ and R₁₂ can jointly form a common aromatic ring with orwithout a hydroxyl group.

R₁₃ and R₁₄ are each independently a hydrogen atom, an alkyl group with1 to 10 carbon atoms, a vinyl group, a phenyl group, a hydroxyphenylgroup, —NH(Formula VI), —N(Formula VI)₂, —NH(Formula VI), —N((FormulaIV)(Formula VI)), —N(Formula VI)₂, or —NH₂.

R₁₅, R₁₆, and R₁₇ are each independently a hydrogen atom, an alkyl groupwith 1 to 10 carbon atoms, a vinyl group, a phenyl group, ahydroxyphenyl group, —NH(Formula VI), —N(Formula VI)₂, —NH(Formula VII),—N(Formula VI)(Formula VII), —N(Formula VII)₂, or —NH₂.

In the Formulas above, each m is independently from 1 to 10, each n isindependently from 0 to 10, each x is independently from 1 to 2, andeach x′ is independently from 0 to 2. Monomers depicted by m and n canbe arranged in any order, combination, or sub-combination.

The alkoxylated triazine-arylhydroxy-aldehyde condensates generally havea nitrogen content of from 0.5 weight percent to 40 weight percent, andfrom 5 weight percent to 15 weight percent in various other embodiments.

One example of the alkoxylated triazine-arylhydroxy-aldehyde condensateis represented by Formula VIII, below:

Another example of the alkoxylated triazine-arylhydroxy-aldehydecondensate is represented by Formula IX, below:

Another example of the alkoxylated triazine-arylhydroxy-aldehydecondensate is represented by Formula X, below:

Another example of the alkoxylated triazine-arylhydroxy-aldehydecondensate is represented by Formula XI, below:

Another example of the alkoxylated triazine-arylhydroxy-aldehydecondensate is represented by Formula XII, below:

Another example of the alkoxylated triazine-arylhydroxy-aldehydecondensate is represented by Formula XIII, below:

Another example of the alkoxylated triazine-arylhydroxy-aldehydecondensate is represented by Formula XIV, below:

Another example of the alkoxylated triazine-arylhydroxy-aldehydecondensate is represented by Formula XV, below:

Another example of the alkoxylated triazine-arylhydroxy-aldehydecondensate is represented by Formula XVI, below:

The alkoxylated triazine-arylhydroxy-aldehyde condensates of thisinvention generally have a viscosity in a solvent in the range of fromabout 1 Pascal second to 1,700 Pascal seconds at 25° C. Any and allranges within 1 to 1,700 Pascal seconds are included herein anddisclosed herein, for example, the alkoxylatedtriazine-arylhydroxy-aldehyde condensates in solvents can have aviscosity in the range of from 10 to 1,500 Pascal seconds or from 100 to1,000 Pascal seconds at 25° C.

The alkoxylated triazine-arylhydroxy-aldehyde condensates of thisinvention can be used as polyisocyanate-reactive compounds to makepolyurethanes and polyisocyanurate-based polymers.

In various embodiments, a reaction mixture is formed with at least onealkoxylated triazine-arylhydroxy-aldehyde condensate and at least onepolyisocyanate. Examples of polyisocyanates that can be used include,but are not limited to m-phenylene diisocyanate,toluene-2,4-diisocyanate, toluene-2,6-diisocyanate,hexamethylene-1,6-diisocyanate, tetremethylene-1,4-diisocyanate,cyclohexane-1,4-diisocyanate, hexahydrotoluene diisocyanate,naphthylene-1,5-diisocyanate, methoxyphenyl-2,4-diisocyanate,diphenylmethane-4,4′-diisocyanate, 4,4′-biphenylene diisocyanate,3,3′-dimethoxy-4,4′-biphenyl diisocyanate, 3,3′-dimethyl-4,4′-biphenyldiisocyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate,4,4′,4″-triphenyl methane triisocyanate, a polymethylenepolyphenylisocyanate, polymeric diphenylmethane diisocyanate (PMDI),isophorone diisocyanate, toluene-2,4,6-triisocyanate and4,4′-dimethyldiphenylmethane-2,2′,5,5′-tetraisocyanate. In variousembodiments, the polyisocyanate is diphenylmethane-4,4′-diisocyanate,diphenylmethane-2,4-diisocyanate, hexamethylene-1,6-diisocyanate,isophorone diisocyanate, toluene-2,4-diisocyanate,toluene-2,6-diisocyanate or mixtures thereof.Diphenylmethane-4,4′-diisocyanate, diphenylmethane-2,4-diisocyanate andmixtures thereof are generically referred to as MDI and all can be used.Toluene-2,4-diisocyanate, toluene-2,6-diisocyanate and mixtures thereofare generically referred to as TDI and all can be used.

Any of the foregoing polyisocyanates can be modified to includeurethane, urea, biuret, carbodiimide, allophonate, uretonimine,isocyanurate, amide, or like linkages. Examples of modified isocyanatesof these types include various urethane group and/or ureagroup-containing prepolymers and so-called ‘liquid MDI’ products and thelike.

In various embodiments, the polyisocyanate can be a blocked isocyanate,where a standard polyisocyanate is prereacted with a blocking agentcontaining active hydrogen groups, which can then be deblocked attemperatures greater than 40° C. (typically in the range of from 100° C.to 190° C.). Examples of blocking agents include, but are not limited toγ-caprolactam, phenol, methyl ketone oxime, 1,2,4-triazole, and dimethylmalonate.

Polyols which can be used in conjunction with the alkoxylatedtriazine-arylhydroxy-aldehyde condensate include polyether polyols.These are prepared by polymerizing an alkylene oxide onto an initiatorcompound that has multiple active hydrogen atoms. Suitable initiatorcompounds include, but are not limited to alkylene glycols, glycolethers, glycerine, trimethylolpropane, sucrose, glucose, fructose,ethylene diamine, hexamethylene diamine, diethanolamine,monoethanolamine, piperazine, aminoethylpiperazine, diisopropanolamine,monoisopropanolamine, methanol amine, dimethanol amine, and toluenediamine.

Polyester polyols can also be used as part of the isocyanate-reactivecompound. Polyester polyols include reaction products of polyols,usually diols, with polycarboxylic acids or their anhydrides, usuallydicarboxylic acids or dicarboxylic acid anhydrides. The polycarboxylicacids or anhydrides can be aliphatic, cycloaliphatic, aromatic, and/orheterocyclic.

Mannich base polyols, which are synthesized from Mannich bases, can alsobe used as part of the isocyanate-reactive compound.

In various embodiments, the alkoxylated triazine-arylhydroxy-aldehydecondensate is present in the isocyanate-reactive compound in a range offrom about 5 weight percent to about 50 weight percent. Any and allranges between 5 and 50 weight percent are included herein and disclosedherein; for example, the alkoxylated triazine-arylhydroxy-aldehydecondensate can be present in the isocyanate-reactive compound in a rangeof from 5 weight percent to 35 weight percent, from 15 weight percent to25 weight percent, or from 9 weight percent to 21 weight percent.

In various embodiments, the alkoxylated triazine-arylhydroxy-aldehydecondensate can also act as a catalyst. Therefore, no extra catalyst isnecessary for the reaction of the alkoxylatedtriazine-arylhydroxy-aldehyde condensate and polyisocyanate compound.

Optionally, in various embodiments, the polyisocyanate and alkoxylatedtriazine-arylhydroxy-aldehyde condensate mixture can also include acatalyst. Examples of catalysts include, but are not limited to tertiaryamines such as dimethylbenzylamine, 1,8-diaza(5,4,0)undecane-7,pentamethyldiethylenetriamine, dimethylcyclohexylamine, and triethylenediamine. Potassium salts such as potassium acetate and potassium octoatecan also be used as catalysts. In various embodiments, the alkoxylatedtriazine-arylhydroxyl-aldehyde condensate can also act as a catalyst.

In various embodiments, the alkoxylated triazine-arylhydroxy-aldehydecondensate also contains a diluent. Examples of diluents include, butare not limited to polyglycols such as ethylene glycol, glycerol, ordiethylene glycol, etherified polyglycols such as monomethyl ether ofethylene glycol or dimethyl ether of ethylene glycol, and dibasic estersof acids such as diethyl adipate, dimethyl adipate, diethyl succinate,or dimethyl succinate. Mixtures of any of these diluents can also beused.

Depending upon the particular type of polymer being produced and thenecessary attributes of the polymer, a wide variety of additionalmaterials can be present during the reaction of the polyisocyanatecompound with the alkoxylated triazine-arylhydroxy-aldehyde condensate.These materials include but are not limited to surfactants, blowingagents, cell openers, fillers, pigments and/or colorants, desiccants,reinforcing agents, biocides, preservatives, antioxidants, flameretardants, and the like.

If a flame retardant is included, the flame retardant is can be aphosphorus-containing flame retardant. Examples of phosphorus-containingflame retardants include, but are not limited to triethyl phosphate(TEP), triphenyl phosphate (TPP), trischloropropylphosphate,dimethylpropanephosphate, resorcinol bis(diphenylphosphate) (RDP),bisphenol A diphenyl phosphate (BADP), and tricresyl phosphate (TCP),dimethyl methylphosphonate (DMMP), diphenyl cresyl phosphate andaluminium diethyl phosphinate.

The relative amounts of polyisocyanate and alkoxylated triazinearylhydroxy aldehyde condensate are selected to produce a polymer. Theratio of these components is generally referred to as the ‘isocyanateindex’ which means 100 times the ratio of isocyanate groups toisocyanate-reactive groups provided by the alkoxylatedtriazine-arylhydroxy-aldehyde condensate. The isocyanate index isgenerally at least 50 and can be up to 1000 or more. Rigid polymers suchas structural polyurethanes and rigid foams are typically made using anisocyanate index of from 90 to 200. When flexible or semi-flexiblepolymers are prepared, the isocyanate index is generally from 70 to 125.Polymers containing isocyanurate groups are often made at isocyanateindices of at least 150, up to 600 or more.

To form the polymer, the polyisocyanate compound and the alkoxylatedtriazine-arylhydroxy-aldehyde condensate are mixed and cured. The curingstep is achieved by subjecting the reaction mixture to conditionssufficient to cause the polyisocyanate compound and alkoxylatedtriazine-arylhydroxy-aldehyde condensate to react to form the polymer.

The polymer formed by the process of this invention can generally have aburn rate in the range of from 50 percent to 60 percent lower than apolyurethane composition that was not prepared with an alkoxylatedtriazine-arylhydroxy-aldehyde condensate. The polymer can also have aweight retention after burning in the range of from 70 percent to 115percent higher, than a polyurethane composition that was not preparedwith an alkoxylated triazine-arylhydroxy-aldehyde condensate.Additionally, the polymer can have a compressive strength at yield inthe range of from 25 percent to 60 percent higher than a polyurethanecomposition that was not prepared with an alkoxylatedtriazine-arylhydroxy-aldehyde condensate.

A wide variety of polymers can be made in accordance with the inventionthrough the proper selection of particularalkoxylated-triazine-arylhydroxy-aldehyde condensates, particularpolyisocyanates, the presence of optional materials as described below,and reaction conditions. The process of the invention can be used toproduce polyurethane and/or polyisocyanurate polymers of various types,including polyurethane foams, sealants and adhesives (includingmoisture-curable types), hot-melt powders, wood binders, castelastomers, flexible or semi-flexible reaction injection molded parts,rigid structural composites, flexible polyurethane foams, binders,cushion and/or unitary backings for carpet and other textiles,semi-flexible foams, pipe insulation, automotive cavity sealing,automotive noise and/or vibration dampening, microcellular foams such asshoe soles, tire fillers and the like. These polymers can then be usedto manufacture articles.

EXAMPLES

The triazine-arylhydroxy-aldehyde condensates used in Examples 1-8 canbe represented as in Formulas XVII and XVIII, below:

These compositions were prepared using methods described in U.S. Pat.No. 9,249,251. Yield is calculated as the total sum of weight added tothe flask minus the total weight of CO₂ expected to be lost.

Example 1

103 grams of triazine-arylhydroxy-aldehyde condensate, 88 grams ofethylene carbonate, and 4 g potassium carbonate were charged to a 250 mL3 necked round bottom flask equipped with mechanical agitator, refluxcondenser, thermocouple, and thermocouple controlled heating mantle. Themixture was heated to 160° C. and was held for 4-6 hours or untilevolution of CO₂ had ceased and was then vacuum distilled to removewater. The yield was 95%.

Example 2

103 grams of triazine-arylhydroxy-aldehyde condensate and 88 grams ofethylene carbonate were charged to a 250 mL 3 necked round bottom flaskequipped with mechanical agitator, reflux condenser, thermocouple, andthermocouple controlled heating mantle. The mixture was heated to 160°C. and was held for 4-6 hours or until evolution of CO₂ had ceased andwas then vacuum distilled to remove water. The yield was 95%.

Example 3

103 grams of triazine-arylhydroxy-aldehyde condensate were charged to a250 mL 3 necked round bottom flask equipped with mechanical agitator,reflux condenser, thermocouple, and thermocouple controlled heatingmantle. The triazine-arylhydroxy-aldehyde condensate was heated to 160°C. and 88 grams of ethylene carbonate was fed to the flask over a periodof 1 hour. The mixture was then held at a temperature of 160° C. for 4-6hours or until the evolution of CO₂ had ceased. It was then vacuumdistilled to remove water. The yield was 95%.

Example 4

103 grams of triazine-arylhydroxy-aldehyde condensate were charged to a250 mL 3 necked round bottom flask equipped with mechanical agitator,reflux condenser, thermocouple, and thermocouple controlled heatingmantle. After the triazine-arylhydroxy-aldehyde condensate was heated to160° C., 44 grams of ethylene carbonate was fed to the flask over aperiod of 1 hour. The mixture was then held at a temperature of 160° C.for 4-6 hours until the evolution of CO₂ had ceased. It was then vacuumdistilled to remove water. The yield was 95%.

Example 5

103 grams of triazine-arylhydroxy-aldehyde condensate were charged to a250 mL 3 necked round bottom flask equipped with mechanical agitator,reflux condenser, thermocouple, and thermocouple controlled heatingmantle. After the triazine-arylhydroxy-aldehyde condensate was heated to160° C., 102 grams of propylene carbonate was fed to the flask over aperiod of 1 hour. The mixture was then held at a temperature of 160° C.for 4-6 hours until the evolution of CO₂ had ceased. It was then vacuumdistilled to remove water. The yield was 95%.

Example 6

828 grams of triazine-arylhydroxy-aldehyde condensate was charged to a 3L 4 necked round bottom flask equipped with mechanical agitator, refluxcondenser, thermocouple, and thermocouple controlled heating mantle andheated to 160° C. Then 408 grams of propylene carbonate and 352 g ofethylene carbonate were fed over 1 hour as a mixture to the moltentriazine-arylhydroxy-aldehyde condensate. The mixture was then held at atemperature of 160° C. for 4-6 hours or until evolution of CO₂ hadceased. The mixture was then vacuum distilled to remove any remainingvolatiles or trace water. The yield was 95%.

Example 7

828 grains of triazine-arylhydroxy-aldehyde condensate and 3.5 grams ofpotassium carbonate were charged to a 3 L 4 necked round bottom flaskequipped with mechanical agitator, reflux condenser, thermocouple, andthermocouple controlled heating mantle and heated to 160° C. Then 408grams of propylene carbonate and 352 grams of ethylene carbonate werefed over 1 hour as a mixture to the molten triazine-arylhydroxy-aldehydecondensate. The mixture was then held at a temperature of 160° C. for4-6 hours or until evolution of CO₂ had ceased. 7 grams of salicylicacid was then charged, and mixing continued for 10 minutes. The mixturewas then vacuum distilled to remove water. The yield was 95%.

Example 8

240 grams of triazine-arylhydroxy-aldehyde condensate and 1.5 grams ofpotassium carbonate were charged to a 1 L 4 necked round bottom flaskequipped with mechanical agitator, reflux condenser, thermocouple, andthermocouple controlled heating mantle and heated to 160° C. Then 204grams of propylene carbonate and 176 grams of ethylene carbonate werefed over 1 hour as a mixture to the molten triazine-arylhydroxy-aldehydecondensate. The mixture was then held at a temperature of 160° C. for4-6 hours or until evolution of CO₂ had ceased. 3 grams of salicylicacid was charged to the reaction mixture, and mixing continued for 10minutes. The mixture was then vacuum distilled to remove water. Theyield was 95%.

Example 9

The alkoxylated triazine-arylhydroxy-aldehyde condensate from Example 3was flaked and fed into a grinding mill and an amount of methylenediphenyl diisocyanate was also fed to achieve a desired isocyanate ratioof 1:1 based on the hydroxyl equivalent weight of thetriazine-arylhydroxy-aldehyde condensate. The composition was ground toa mesh size of 50-100% through 200 mesh. The powdered composition wascured above the melting point or softening point of the resultingmixture to yield a cross-linked polyurethane.

Example 10

20 grams of alkoxylated triazine-arylhydroxy-aldehyde condensate fromExample 4 were dissolved in 20 grams of triethyl phosphate and 10 gramsof ethylene glycol to yield a viscous solution with an approximatehydroxyl equivalent weight of 98. This mixture was further formulatedwith cyclopentane as a surfactant and emulsified. A polymeric isocyanatewas added to achieve a specific isocyanate ratio of 1:1 and then mixedto create a polyurethane foam.

Example 11: Viscosities of Alkoxylated Triazine-Arylhydroxy-AldehydeCondensates

An ARES-G2 rheometer (TA Instruments) equipped with stainless steelparallel plates was operated under rotational mode to determine theviscosities of the formulation from Example 3 at 150° C., 140° C., and130° C. The viscosity was determined from a “zero-shear” approximationin which the viscosity is measured as a function of shear rate (0.1-100l/s). The zero shear viscosity was determined by averaging the viscosityin the Newtonian region, which is approximately 1-100 l/s. Ten datapoints were measured for every magnitude change of shear rate such as 10points between 0.1 and 1 l/s. The lower temperature was determined whenthe materials exhibited non-Newtonian behavior such as shear thinning.The viscosity of triazine-arylhydroxy-aldehyde condensate was comparedwith the viscosity of ethoxylated triazine-arylhydroxy-aldehydecondensate. Results are shown in Table 1 for Examples 3, 5, and 8,below.

TABLE 1 Viscosity Results Viscosity of Viscosity of Viscosity ofAlkoxylated Tri- Alkoxylated Tri- Alkoxylated Tri- Viscosity of Tri-azine Arylhydroxy- azine Arylhydroxy- azine Arylhydroxy- azineArylhydroxy- Aldehyde Condensate Aldehyde Condensate Aldehyde CondensateTemperature Aldehyde Condensate From Example 3 From Example 8 FromExample 5 (° C.) (Pa · s) (Pa · s) (Pa · s) (Pa · s) 150 6.0 0.18 0.0130.048 140 23 0.32 0.022 0.092 130 117 0.65 .041 0.112

Alkoxylated triazine-arylhydroxy-aldehyde condensates were alsodissolved in solvents after which viscosity was measured using themethod described above. Tables 2, 3, and 4 show viscosity results forsamples at 50° C., 40° C., 30° C., and 25° C.

TABLE 2 Viscosity Results for Example 3 in Diethylene Glycol (DEG)Viscosity Viscosity Viscosity Viscosity at 50° C. at 40° C. at 30° C. at25° C. % DEG (Pa · s) (Pa · s) (Pa · s) (Pa · s) 20 5.62 18.14 77.64168.09 31 0.75 1.78 4.98 8.45 40 0.33 0.71 1.74 2.77 50 0.15 0.27 0.580.95 61 0.07 0.11 0.21 0.31

TABLE 3 Viscosity Results for Example 8 in Triethyl Phosphate (TEP)Viscosity Viscosity Viscosity Viscosity at 50° C. at 40° C. at 30° C. at25° C. % TEP (Pa · s) (Pa · s) (Pa · s) (Pa · s) 22 2.49 8.22 30.0571.06 31 0.64 1.68 4.96 9.68 41 0.13 0.26 0.56 0.89 51 0.04 0.06 0.090.13

TABLE 4 Viscosity Results for Example 8 in Diethylene Glycol (DEG)Viscosity Viscosity Viscosity Viscosity at 50° C. at 40° C. at 30° C. at25° C. % DEG (Pa · s) (Pa · s) (Pa · s) (Pa · s) 17 28.28 133.19 888.131641.36 25 5.13 17.50 72.94 156.06 50 0.13 0.26 0.54 0.92 40 0.42 0.972.64 4.44 30 0.94 2.41 7.46 13.52

Based upon the results of Tables 1-4, an alkoxylatedtriazine-arylhydroxy-aldehyde condensate can be used as a rheologymodifier for polyurethane crosslinking systems.

Example 12: Effect of Introducing AlkoxylatedTriazine-Arylhydroxy-Aldehyde Condensate Into a typical PU Formulationfor Rigid Foams

As a first step, a reference polyurethane mixture (Reference Formulation#1) and test polyurethane mixtures (Test Formulations #1 and #2) wereprepared using the two formulations shown in Table 5, below. Thealkoxylated triazine-arylhydroxy-aldehyde condensate of the currentinvention was mixed into the reference carbohydrate-based aliphaticpolyol (Reference Polyol #1) at a 80:20 ratio of Reference Polyol #1 tothe ethoxylated condensate from Example 3 along with other componentslisted in the Table, at 100° C. in a cup at 2200 RPM using Speed MixerDAC 400 FV. To form Reference Formulation #1, Reference Polyol #1 wasblended with other components in the same manner as described above. Toform Test Formulation #2, Reference Polyol #1 was blended with aconventional aromatic-based polyol and the ethoxylated condensate ofExample 3.

These polyol mixtures were then mixed with Rubinate M, a polyisocyanate,to an isocyanate index of 110% to form a free-rise foam. The actualmixing technique and equipment used are described below in detail under‘Method to Prepare Foam Samples for Flame and Mechanical Tests’. Thereactivity differences between the two formulations are measured as themix time, cream time, gel time, rise time and tack-free time as shown inTable 5.

Method to Prepare Foam Samples for Flame and Mechanical Tests

Foams were prepared using a high-torque mixer (CRAFTSMAN 10-Inch DrillPress, Model No. 137.219000) at 3,100 rpm speed. Polyol components andisocyanate components of the foam systems were mixed for 10 seconds.Afterwards, the mixture was transferred into an open cake box before thecream time and was allowed to rise. Two sets of foams were preparedusing 50 grams and 100 grams of total polyols, respectively. Foams with50 grams of total polyols were prepared by pouring the foaming mix intocake boxes of 6″×6″×3″ dimensions and those with 100 grams of totalpolyols were prepared by pouring the mix into cake boxes of 12″×12″×4″dimensions. Foams prepared with 100 grams of total polyols were used fortesting of density, flammability, and compressive strength propertiesand foams prepared with 50 grams were used for reactivity comparisons.

Description of Materials:

Dabco® DC193, a silicone surfactant available from Evonik.

Dabco® 33LV, an amine catalyst available from Evonik.

Niax A-1, a catalyst available from Momentive Performance Materials.

Rubinate® M, a polymeric MDI isocyanate, available from Huntsman.

TABLE 5 Properties of Formulations Reference Test Test FormulationFormulation Formulation #1 # 1 # 2 Ref Polyol #1 (carbohydrate- 100 8070 based aliphatic polyol), g Ref Polyol #2 (aromatic 0 0 21 polyol), gEthoxylated Triazine- 0 20 9 arylhydroxy-aldehyde condensate, g Water, g4.5 4.5 4.5 Dabco DC193, g 2 2 2 Dabco 33LV, g 1.8 1.8 1.8 Niax A-1, g0.1 0.1 0.1 Rubinate M, g 172.99 176.03 182.16 Residual water, g 0.020.02 0.07 Isocyanate Index 110% 110% 110% Reaction profile of free-risefoams Mix time, s 10 10 10 Cream time, s 22 18 20 Gel time, s 67 43 45Rise time, s 98 75 73 Tack-free time, s 116 78 75

Example 13: Fire Resistance and Mechanical Properties Physical andMechanical Property Testing Methods

Core Density, pcf Method: ASTM D 1622-03

Compressive Strength, psi: ASTM D 1621-00

Compressive Strain @ Yield %: ASTM D 1621-00

Flame Test: The burning rate and weight retention after burning weremeasured using a modified ASTM D 4986 flammability test. According toASTM 4986, a specific burner is used and is defined by ASTM D5025 and agas with a heat content of 37±1 MJ/m³. In the modified test herein, aBernzomatic torch TS4000, which heats to 1982° C. in air was used.Specimen sizes and calculation of the burning rates are identical to theASTM D 4986 method. The flame source is removed at the time when theflame reaches the first mark line on the specimen. According to ASTM D4986, one set of five specimens are conditioned for at least 48 hours at23° C. and relative humidity of 50±5% prior to testing. The second setof five specimens are conditioned in an air circulating oven for 168±2 hat 70±2° C., and then cooled in a desiccator for at least 4 hours atroom temperature prior to testing. In the modified test, 6 specimens arecut prior to testing from foam aged at room conditions (ambienttemperature and humidity) for a minimum of 7 days after preparation ofthe foam.

Table 6, below shows properties of foams prepared using three differentformulations. One reference formulation used a carbohydrate-basedaliphatic polyol. The two test formulations (#3 and #4) are preparedfrom various amounts of the carbohydrate-based aliphatic polyol, aconventional aromatic-based polyol, and the ethoxylatedtriazine-arylhydroxy-aldehyde condensate of Example 3. Theseformulations were prepared as described in Example 12, above.

As can be seen from Table 6, foams prepared from the alkoxylatedtriazine-arylhydroxy-aldehyde condensate provided slower burn rates,higher weight retentions, and good mechanical properties. Thecompressive strength at yield and the compressive strength at maximumload significantly increased with the introduction of the alkoxylatedtriazine-arylhydroxy-aldehyde condensate into the formulation. Ingeneral, the compressive strength is dependent on the foam density.However, this increase in the compressive strength with introduction ofalkoxylated triazine-arylhydroxy-aldehyde condensate into theformulation is much greater than the possible effect of an increase inthe foam density. The compressive strengths at yield and at maximum loadof foams containing alkoxylated triazine-arylhydroxy-aldehydecondensate, when normalized to the density of the reference foam of 1.98pcf, are significantly higher than that of the reference foams.Therefore, the observed effect of alkoxylatedtriazine-arylhydroxy-aldehyde condensates on compressive strength issignificant.

It is important to note that the compressive strain at yield was notaffected significantly with the introduction of the alkoxylatedtriazine-arylhydroxy-aldehyde condensate, which indicates the overallrigidity (friability) of the foams was not significantly affected.

As can be seen in both Tables 5 and 6, polymers prepared withalkoxylated triazine-arylhydroxy-aldehyde condensates have cream timesthat are about 4 to 19 percent lower, gel times that are about 35 to 42percent lower, rise times that are about 23 to 34 percent lower, andtack-free times that are about 32 to 43 percent lower than the referenceformulation that was not prepared with an alkoxylatedtriazine-arylhydroxy-aldehyde condensate. This indicates that foamsprepared from the alkoxylated triazine-arylhydroxy-aldehyde condensatehave higher reactivites than the foam prepared from the referenceformulation.

As can be seen in Table 6, as the quantity of the alkoxylatedtriazine-arylhydroxy-aldehyde condensate component in the formulationsincreased from 0% to 15% and then to 21%, the burn rate continued todrop further and the weight retention increased, which indicatessuperior fire retardant characteristics when compared the to thereference formulation. The superior fire retardant characteristics ofalkoxylated triazine-arylhydroxy-aldehyde condensates of this inventionare attributed to its relatively high nitrogen and aromatic content.

These results show the effectiveness of the alkoxylatedtriazine-arylhydroxy-aldehyde condensates of the current invention asflame retardants in polyurethane rigid foam formulations and theirpotential use in other polyurethane applications as well.

TABLE 6 Mechanical and Flame Properties of Reference vs. TestFormulations Reference PU Test PU Test PU Formulation FormulationFormulation #1 # 3 # 4 Ref Polyol #1- 100 50 30 carbohydrate-basedaliphatic polyol, g Ref Polyol #2-aromatic 0 35 49 polyol, g Ethoxylatedtriazine- 0 15 21 arylhydroxy-aldehyde condensate, g Water, g 4.5 4.54.5 Dabco DC193, g 2.0 2.0 2.0 Dabco 33LV, g 1.8 1.8 1.8 Niax A-1, g 0.10.1 0.1 Rubinate M, g 172.99 187.79 193.43 Residual water, g 0.02 0.110.14 Isocyanate Index 110%   110%   110% Density, pcf  1.98 ± 0.01  2.17± 0.05  2.37 ± 0.06 Mix time, s 10 10 10 Cream time, s 22 19 21 Geltime, s 67 41 39 Rise time, s 98 68 65 Tack-free time, s 116 70 67Compressive Strength at 24.4 ± 1.8 30.8 ± 2.2 39.0 ± 2.7 Yield, psiCompressive Strain at  6.9 ± 2.6  5.8 ± 0.7  9.1 ± 2.7 Yield, %Normalized Compressive 24.4 ± 1.8 28.1 ± 2.0 32.6 ± 2.3 Stress at Yieldto a Density of 1.98 pcf, psi Normalized Compressive 24.9 ± 1.4 28.4 ±2.2 33.9 ± 3.5 Stress at Maximum Load to a Density of 1.98 pcf, psi BurnRate, cm/min 29.6 ± 1.8 14.0 ± 0.4 12.1 ± 0.5 Weight Retention, % 38.2 ±5.6 66.5 ± 7.4 80.4 ± 3.9 Change in Burning Rate n/a −52.70% −59.10%Change in Weight n/a  74.10% 110.50% Retention

The invention claimed is:
 1. A process comprising: forming a reactionmixture containing at least one polyisocyanate and anisocyanate-reactive compound comprising at least one alkoxylatedtriazine-arylhydroxy-aldehyde condensate composition wherein thealkoxylated triazine-arylhydroxy-aldehyde condensate composition is areaction product of a triazine-arylhydroxy-aldehyde condensate and atleast one alkylene carbonate.
 2. A process in accordance with claim 1further comprising curing the reaction mixture to form a polymer.
 3. Theprocess of claim 1 wherein the reaction mixture further comprises aphosphorus-containing flame retardant.
 4. The process of claim 1 whereinthe isocyanate-reactive compound further comprises a diluent selectedfrom the group consisting of ethylene glycol, glycerol, diethyleneglycol, monomethyl ether of ethylene glycol, dimethyl ether of ethyleneglycol, diethyl adipate, dimethyl adipate, diethyl succinate, dimethylsuccinate and combinations thereof.
 5. The process of claim 1 whereinthe polyisocyanate is selected from the group consisting ofdiphenylmethane-4,4′-diisocyanate (4,4 MDI),diphenylmethane-2,4′-diisocyanate (2,4 MDI), toluene-2,4-diisocyanate,toluene-2,6-diisocyanate, isophorone diisocyanate,hexamethylene-1,6-diisocyanate, polymeric diphenylmethane diisocyanate(PMDI) and combinations thereof.
 6. The process of claim 1 wherein thepolyisocyanate is a blocked isocyanate.
 7. The process of claim 2wherein the polymer is prepared with an isocyanate-reactive compoundhaving from 9 weight percent to 21 weight percent of the alkoxylatedtriazine-arylhydroxy-aldehyde condensate.
 8. The process of claim 7wherein the polymer has a cream time that is from 4 percent to 19percent lower than a polymer that was not prepared with an alkoxylatedtriazine-arylhydroxy aldehyde condensate.
 9. The process of claim 7wherein the polymer has a gel time that is from 32 percent to 42 percentlower than a polymer that was not prepared with an alkoxylatedtriazine-arylhydroxy aldehyde condensate.
 10. The process of claim 7wherein the polymer has a rise time that is from 23 percent to 34percent lower than a polymer that was not prepared with an alkoxylatedtriazine-arylhydroxy aldehyde condensate.
 11. The process of claim 7wherein the polymer has a tack-free time that is from 32 percent to 43percent lower than a polymer that was not prepared with an alkoxylatedtriazine-arylhydroxy aldehyde condensate.
 12. The process of claim 7wherein the polymer has a burn rate in the range of from 50 percent to60 percent lower than a polyurethane composition that was not preparedwith an alkoxylated triazine-arylhydroxy-aldehyde condensate.
 13. Theprocess of claim 7 wherein the polymer has a weight retention afterburning in the range of from 70 percent to 115 percent higher than apolyurethane composition that was not prepared with an alkoxylatedtriazine-arylhydroxy-aldehyde condensate.
 14. The process of claim 7wherein the polymer has a compressive strength at yield in the range offrom 25 percent to 60 percent higher than a polyurethane compositionthat was not prepared with an alkoxylated triazine-arylhydroxy-aldehydecondensate.
 15. The process of claim 2 wherein the polymer is apolyurethane or polyisocyanurate foam.
 16. The process of claim 2wherein the polymer is a wood binder.
 17. An article prepared from thepolyurethane or polyisocyanurate foam of claim
 15. 18. An articleprepared from the wood binder of claim
 16. 19. An article prepared fromthe process of claim 6.